Chemical method of liquefaction and dispersion of paraffin waxes, asphaltenes and coke derived from various sources

ABSTRACT

A chemical composition comprising selected surfactants, dispersants, and degreasers that liquefy, disperse, demulsify, degrease, inhibit corrosion and scale formation, and lower the pour point of a petroleum, coal, Fischer-Tropsch synthesized, or naturally occurring paraffin-based wax and asphaltene. The composition preferably contains (1) a mixture of oil soluble, surface active polyethoxylated compounds; (2) a mixture of organic solvents (non-hydrocarbon) used as degreasing agents, pine oil, and butyl cellusolve; (3) a mixture of oil- and water-soluble dispersing copolymers of partially sulfonated, maleic anhydride and polystyrene with a molecular weight ranging from about 2,000 to about 2,000,000; and (4) a mixture of saturated higher fatty acids and an alkyl-phenolic based compound acting as corrosion inhibitors. Such a product is capable of converting crystalline wax (paraffin) in, for example, slop oil into an amorphous form of wax at room temperature, allowing the wax to be dissolved in, for example, crude oil without the need for heating, and maintaining it in solution at room temperature, substantially reducing, indeed in some applications, preventing, for example, wax build-up in pipelines, processing and transportation equipment, etc., and the recovery of the hydrocarbons in the slop oil. The surface active agent of the composition achieves this, it is believed, by reducing the surface tension of the wax. The preferred combined composition preferably also provides effective corrosion &amp; scale formation inhibitors (protection), demulsifiers, degreasers and pour point &amp; cloud point depressants.

TECHNICAL FIELD

The present invention relates generally to converting crystalline wax,as, for example, exists in slop oil, to an amorphous form of wax,causing it to be dissolvable in, for example, crude oil at, for example,ambient temperature and maintained in a dissolved state for a prolongedperiod of time at ambient temperature, and more particularly, in itspreferred, exemplary embodiment, to the use preferably of a chemicalcomposition of surfactants, polymeric dispersants and corrosion & scaleformation inhibitors that can, for example, recover waste hydrocarbonproducts (paraffin waxes, asphaltenes, and coke) from bothnaturally-occurring and synthetic sources, and more particularly torecover these waste hydrocarbon products for use as energy sources andto reduce environmental pollution. A number of other applications isalso disclosed and claimed.

BACKGROUND ART

Waxy materials present in crude oils and in the high boiling fractionsare considered to be crystalline throughout but under certain conditionsmay behave like a colloid. Certain wax solutions of refined productssuch as petrolatum, when agitated or mixed for long periods near or atthe crystallizing temperature, will form a completely transparent jelly.But the same solution, when chilled rapidly with moderate agitation willprecipitate a wax that can be centrifuged.

It was observed many years ago in the sweating of solid paraffins at thepetroleum refinery that three crystalline forms (manifestations) ofhydrocarbons are involved. These are known as “plate”, “malcrystal”, and“needle”[note, for example, The Chemistry and Technology of Waxes buAlbin H. Warth, published by Reinhold Publishing Corp. (New York, 1947)p. 239]. It was recognized that the relative proportion of these typesof crystals not only has a relationship to the source of the crude butalso to the process of handling the wax.

The members of each series crystallize similarly as either plates,malcrystals, or needles. If one type is present (plate, mal, or needle),the crystal form remains the same regardless of such factors as theamount and kind of solvent.

When crude oil is pumped from the ground and transported throughpipelines, transported by ocean tankers, or stored in storage tanks onland or offshore, a large amount of heavy material separates and comesout of solution. The main component of this residue is high molecularweight paraffin waxes. In some cases the wax represents as much as 90percent of the deposited residues.

The amounts of wax present in crude oil are to a large extent anindicator of its origin, whether the crude originated in Venezuela,Mexico, or Malaysia.

This mixture of wax, oil, sand, and water is referred to as “slop oil”,or “slop”, in the petroleum industry. The percentage of slop oil variesaccording to the type of crude and the conditions under which it hasbeen transported. Usually the amount of slop oil ranges from a low of0.5% to a high of 10%; normally, it is in the range of 2% to 5%.

For the last century and until today the only way to keep slop oil fromseparating from crude oil is to heat the slop oil while it is beingtransferred into mixing tanks with crude oil. The cost of keeping slopoil mixed with crude oil is a function of many variables such astemperature, solvent diluents, and residence time of the crude in a tankor pipeline.

The petroleum industry is plagued with the problem of having to delivercrude oil to refineries in a timely and economic manner. If a pipelinebecomes plugged up or clogged because of paraffin wax precipitating outduring the pumping operation, a crisis can arise. Numerous pipelinesworldwide are clogged daily or monthly due to wax precipitating out ofthe crude oil. Daily, 50,000,000 barrels of crude oil are pumped fromthe ground worldwide (as of May, 1999). If 5% of the heavy residues comeout of the crude oil being transported, whether by pipeline or tanker,the amount of slop oil or crude residue is 2,500,000 barrels per day.This amounts to 912,000,000 barrels per year. If 70% of this slop oil isuseable crude which can be processed to refine production, then theamount of recoverable hydrocarbon equals over 640,000,000 barrels peryear. At a cost of $10.00/barrel of crude oil this amounts to therecovery of $6.4 billion per year of useable hydrocarbon as eitherenergy or petrochemical feedstock.

Another important factor in the transportation of crude oil is thecorrosion of pipelines, storage tanks, and marine tankers. One of themain sites of corrosion in pipelines and storage tanks is at the pointof buildup of the paraffin wax. At this site corrosion-causing chemicalsbecome embedded in the wax and migrate to the metal surfaces. Pipelineswith intrinsically large wax buildup or settling have many morecorrosion problems than pipelines where the oil moves swiftly withoutdeposition occurring. This results in increased maintenance cost and insome cases pipelines have to be shut down and crude must be rerouted tonew lines as a result of both the clogged lines and corrosion. One ofthe main maintenance tools used to unclog crude oil pipelines is piggingthe line. In this process a small device shaped like a pig with a seriesof scrapers on its sides is shot through the line to remove all the wax.This wax is then collected at traps located along the line and shippedto pipeline pumping stations for storage.

In storage tanks the problems associated with wax settling out aretremendous and present an extremely challenging task to refiners andterminal operators.

When crude oil remains idle and cold in a storage tank, a heavy residueforms that, over time, accumulates at the bottom of the tank and reducesuseable tank volume. This residue, known as slop oil (or, slop),consists of heavy paraffinic waxes and asphaltenes which solidify incrystalline form. Slop oil is extremely difficult to remove from tanksand presents a very costly disposal problem for the refinery andterminal operator.

Traditional tank cleaning methods use a combination of heat (e.g., 60 to75 degrees C. or greater) and mechanical agitation to force the slop oilback into solution with crude oil, so the mixture can be pumped out ofthe tank. In order to keep the waxes and asphaltenes in solution withthe crude oil, the mixture must be kept at, for example, 75 degrees C.or greater and, in most cases, continuously circulated. The tremendousamounts of energy required to heat and circulate large volumes of densecrude oil to these elevated temperatures over long periods of timeincrease handling costs dramatically.

After pumping out the slop oil containing paraffin waxes andasphaltenes, the slop oil mixture must be kept hot or the wax willseparate from solution, and the problems associated with slop oil willrecur.

This need to use heat results in great energy cost and losses.

The preferred, exemplary chemical compound mixture described herein willperform, inter alia, the following functions:

1. Converts the wax in, for example, the slop oil from a crystalline toan amorphous material;

2. Disperses the amorphous material into a diluent solvent;

3. Acts as a demulsifier which separates any water present in the slopoil;

4. Acts as a degreaser and works at a very low activity, e.g., 0.025%;and

5. Acts as a pour point depressant.

Since it acts as a wax liquefier and converts the wax to a lesscrystalline and more amorphous form, the slop oil waxes are readilydispersible into the crude oil medium. Thus a colloid is formedconsisting of heavy paraffin wax and asphaltene compounds dispersed incrude oil. Since the preferred, exemplary composition of matterdescribed herein also acts as a demulsifier, all water present in theslop oil mixture separates out, as well as the sand or grit present. Theheavy paraffin wax and asphaltenes are dispersed as hydrocarbon into thecrude oil and can be, for example, transported to the refinery forprocessing or to a marine tanker or other transport for shipment, forexample, at ambient temperature.

The use of the preferred, exemplary composition of matter describedherein, when, for example, injected into crude oil pipelines at, forexample, the production source, is capable of keeping the heavy wax andasphaltenes dispersed in the crude oil. Having the wax and asphaltenesdispersed 100% into the crude oil will accomplish at least thefollowing:

1. Lower maintenance costs by reducing the need to use costly piggingoperations on pipelines, which requires at least a partial shut-down ofthe pipeline;

2. Lower maintenance costs by reducing the problems associated withcorrosion in pipelines; with both items “1” and “2” reducing the numberof downtime stoppages in the pipeline; and

3. Increase the throughput and flow rate of crude oil through pipelines.

The main goal and objective of a crude oil pipeline company is, forexample, to deliver to their customers a fixed amount of crude on anagreed-to, set schedule; every day that schedule is not met because oftechnical problems, the company loses money.

If the preferred, exemplary composition of matter described herein ismixed with crude oil loaded on, for example, marine tankers, theproblems associated with wax deposits will be at least greatlyinhibited, if not prevented from occurring, namely, slop oil residueswill be greatly reduced and indeed prevented from forming. In, forexample, oceangoing marine tankers the problems are twofold. At the endof many journeys the tankers have to go into drydock for maintenance dueto corrosion caused by slop oil settling out and coating the walls ofthe tanks.

The benefits of the preferred, exemplary chemical composition describedherein can be realized in, for example, the following ways:

1. Recovery of at least 640,000,000 barrels per year of hydrocarbons(based on a daily production of 50,000,000 barrels), which results in ayearly recovery value of approximately $6.4 billion at a world crude oilprice of $10.00/barrel. At a world crude oil price of $20.00/barrel theyearly recovery value would be $12.8 billion;

2. The projected cost for use of the composition of matter describedherein as a wax and asphaltene dispersant, liquefying agent, anddemulsifier would range in price at 1999 costs from a low of about$0.05/barrel to a high of about $0.42/barrel, depending on the injectionrate; and

3. The overall maintenance costs associated with pipeline transport,marine tanker transport, and storage tank cleaning could be as much as$0.10/barrel of crude oil produced or $2.0 billion per year.

In addition to the exemplary application of use with crude oil, thereare many other applications of the principles and teachings of thepresent invention, as detailed and exemplified below, all with greatutilitarian benefits.

For general background, “prior art” information pertinent to theinvention, reference is had to:

The Chemistry and Technology of Waxes by Albin H. Warth, published byReinhold Publishing Corp. (New York, 1947), p. 239 et al;

Petroleum Refinery Engineering by W. L. Nelson, published by McGraw-HillBook Co. (New York, 4^(th) Ed., 1958), particularly Chapter 12“DeWaxing”(pp. 374-75 et seq.);

Physical Chemistry by Walter J. Moore, published by Prentice-Hall, Inc.(New York, 1955), particularly Chapter 16 “Surface Chemistry”(p. 498 etseq.); and

chemical and process technology encyclopedia edited by Douglas M.Considine, published by McGraw-Hill Co. (New York, 1974), particularlyits sub-section on “Waxes”(p. 1167 et seq.).

GENERAL SUMMARY DISCUSSION OF INVENTION

The invention described herein in a very important aspect relates to theuse of a composition of matter and an associated mixture that acts as,for example, a paraffin and asphaltene liquefying and dispersing agentand as a dispersing agent for coke and coal fines. The dispersing mediumcan be, for example, a petroleum-based product (such as crude oil or anyrefined petroleum product), a Fischer-Tropsch-based product (such asliquid hydrocarbon products derived from natural gas and byproducts ofnatural gas), coal, town gas, waste gases derived from animal andvegetable wastes, oils and organic solvents derived from agriculturalsources (such as, for example, edible oils, furfural, alcohols, andother organic liquids) and water.

The source of the paraffin being liquefied and dispersed can be from,for example, petroleum, petrochemical, Fischer-Tropsch synthesis(including natural gas, natural gas liquids, coal, coal byproducts—peat,etc.), agricultural sources (carnauba-palm leaves, etc.), and animalsources (e.g., beeswax). The source of the asphaltene being liquefiedand dispersed can be, for example, from petroleum, petrochemical,Fischer-Tropsch synthesis, coal, and shale.

In accordance with this aspect of the invention a method for liquefyingand dispersing paraffin waxes and asphaltene containing, for example,petroleum products, can be dispersed into, for example, crude oil,refined petroleum products (such as diesel, fuel oil, etc.) and othersolvents such as water at room temperature. The dispersions remainstable at ambient temperatures over a long period of time. The preferredprocess of carrying out this invention includes, for example, the simplemixing of waste paraffin waxes and asphaltenes in the presence of crudeoil or any refined petroleum product mixed with the product describedherein at a concentration ranging from about 50 to about 100,000 ppm, ateither, for example, ambient temperature or at an increased temperature,e.g., the melt temperature of the paraffin wax, if so desired, with theoptimum concentration ranging from about 250 to 1,500 ppm.

The dispersion of the paraffin wax and asphaltenes tend to disperse moreeasily at higher temperatures using lower concentrations of chemicaldispersant. The ultimate result of mixing the wax and asphaltene withthe diluent is the same whether it is mixed at ambient temperatures(e.g., 21 degrees C.) or at higher temperatures (e.g., about 60 to about120 degrees C., or higher, if so desired), namely that the wax andasphaltene are dispersed in the diluent, whether, for example, crude oilor other refined products, and stays in solution for at least six (6)months, based on current tests, which are still on-going, if not longer.

Additional advantages of this preferred, exemplary application of theinvention, as well as other applications, will become apparent from thedescription which follows.

In other diluents, such as water, it was found that the wax in greasethat has oxidized for over, for example, three (3) years, can beinstantly liquefied and dispersed in water. The dispersion of the greasein water was passed through a water filtering system, with the endresult being water of a quality acceptable for reuse.

The principles and teachings of the present invention have broadapplicability, and a number of other, exemplary applications are listedbelow.

It is thus an object of the invention to convert crystalline wax to anamorphous form by, for example, reducing its surface tension.

It is a further an object of the invention to convert crystalline wax toan amorphous form suitable for being dissolved in a desired or availablediluent, for example, in crude oil or other hydrocarbon, when dealingwith, for example, slop oil for, for example, recovery of thehydrocarbons in the slop oil and for enhanced transportation andpipeline movement of crude oil.

It is a still further object of the invention to provide a particularlyefficacious dispersant for wax or paraffin, while also preferablyproviding corrosion and scale formation inhibition, demulsifying anddegreasing, with preferably a homogeneous mixture.

It is a still further an object of the invention to provide enhancedcleaning of objects having, for example, a build-up of wax-containingsubstance(s).

It is a still further an object of the invention to provide cloud pointlowering of, for example, lube oil and the like, i.e., dehazing.

It is a still further an object of the invention to provide pour pointlowering of, for example, lube oil and the like.

It is a still further an object of the invention to provide a product orcomposition of matter and associated method for convertingcrystalline-wax-containing substances to an amorphous form in one ormore of the applications detailed below.

For a further understanding of the nature and objects of the presentinvention, reference should be had to the foregoing and the followingdetailed description.

EXEMPLARY MODES Exemplary Composition of Matter or Product

The preferred, exemplary composition of matter or exemplary, currentlypreferred, wax liquefier and dispersant of the invention is ahomogeneous mixture (preferably pure solution, one phase) of

about 25% to about 99.5% by weight of surface active agent,

about 15% to about 35% by weight butyl cellosolve,

about 5% to about 15% by weight of pine oil and a specially mixedcatalyst solution made of saturated higher fatty acids, an alkly phenoland an oil-water soluble copolymer of partially sulfonated, maleicanhydride and polystyrene with a molecular weight ranging from about2,000 to about 2,000,000. The catalyst mixture normally is present in arange of about 0.5% to 5%, with all percentages being “by weight”percentages.

One particularly preferred, exemplary composition is about 48% surfaceactive agent in the form of a nonionic polyethoxylated compound, e.g.,one derived from polyethylene oxide, which has a H.L.B. number of 11.0.

As is known in the surfactant art, an H.L.B. number represents afundamental property of a nonionic surfactant that correlates with bothphysical properties and surface active effects. The H.L.B. number is ameasure of the hydrophilic and lipophilic (hydrophobic) characteristicsof the surfactant molecule. In a series of surfactants prepared by theethoxylation of an alcohol or amine, for example, the ratio ofhydrophilic to lipophilic portions increases with the increasing degreeof ethoxylation. This corresponds to an increase in hydrophiliccharacter—or water solubility—of the molecule. The H.L.B. number of thesurfactant determines the type of emulsion produced as well as thestability of the emulsion. A water-in-oil (W/O) type of emulsionrequires emulsifiers of low H.L.B. number, e.g., about four (4) [100%water insoluble-non-dispersible in water)], while an oil-in-water (O/W)type requires emulsifiers with higher H.L.B. numbers, e.g., nine tosixteen (9-16). Surfactants with H.L.B. numbers near thirteen (13) aredetergents, and those of fifteen to sixteen (15-16) are stabilizers. Thesurface active agents in the currently preferred, exemplary productpreferably have a H.L.B. number ranging from about ten to about elevenand a half (10-11.5) and are considered to be good re-wetting agents(low contact angle) and are good emulsifying and dispersing agents foroils and solids.

Another factor to be considered is the addition of a surface tensiondepressant. In order to enhance the effectiveness of the surface activeagent, for example, a fluorocarbon alcohol is added to lower the surfacetension of the composition of matter. Normally the amount added is, forexample, 0.1%. Therefore, the surface active agent consists of anonionic surfactant that is made up of, for example, about 99.9% of apreferably commercially available, nonionic polyethoxylate surfactantand, for example,about 0.1% of a surface tension depressant in the formof, for example, a flouronated hydrocarbon alcohol. The range of surfacetension for the final composition of matter ranges from about 10 toabout 48 dynes/cm and more preferably from about 15 to about 32 dynesper cm.

The by-weight percent of the nonionic surface active agent is preferablyabout 48%, with about 32% butyl cellosolve and about 17% pine oil (withboth of these latter components acting as a degreaser), about 3% of amixture containing about 70% higher fatty acids, about 29% a copolymerof partially sulfonated, maelic anhydride and polystyrene, and about 1%of catechol (serving as a corrosion inhibitor).

Other surface active agents, which may be used in place of or incombination with the exemplary polyethylene-oxide-based, nonionicsurfactant, are outlined below.

Types of Nonionic Surfactants

- Types of Nonionic Surfactants - H.L.B. # 1. Ethonylated Alcoholstridecyl alcohol ethoxylate (6 EO) 11.4 (where EO is ethlyene oxide)tridecyl alcohol ethoxylate (9 EO) 13.3 tridecyl alcohol ethoxylate (12EO) 14.5 tridecyl alcohol ethoxylate (15 EO) 15.3 Witco Chemicals'tridecyl alcohol ethoxylate 12.4 Stepan Chemicals' tridecyl alcoholethoxylate 12.4 alcohol ethoxylate (3 EO)  8.0 alcohol ethoxylate (6 EO)11.8 alcohol ethoxylate (8 EO) 13.2 alcohol ethoxylate (10 EO) 14.1C₈-C₁₀ alcohol ethoxylate (6 moles) 12.5 C₈-C₁₀ alcohol ethoxylate (8moles) 13.6 2. Reactions of Cocoacid + Polyethylene Glycol (PEG) PEG30 -glyceryl cocoate 15.9 PEG80 - glyceryl cocoate 18.0 PEG30 mixture -glyceryl cocoate 15.9 PEG20 - glyceryl tallowate 13.0 PEG80 - glyceryltallowate 18.0 PEG200 - glyceryl tallowate 19.0 PEG2 cocamine  6.2 PEG5cocamine 11.0 PEG10 cocamine 13.8 PEG15 cocamine 15.4 PEG15 cocaminemixture 15.4 It is noted that, as the amount of ethoxylation increases,the H.L.B. # increases, and the cationic character changes to morenonionic. PEG2 tallow amine  5.1 PEG2 tallow amine mixture  5.1 PEG5tallow amine  9.2 PEG10 tallow amine 12.6 PEG15 tallow amine 14.4 PEG15tallow amine mixture 14.4 PEG20 tallow amine 15.4 3. Other CommerciallyAvailable, Nonionic Surfactants Nonylphenol (5 EO)  6.8 Nonylphenol (10EO) 11.0 Nonylphenol (12 EO) 12.2 Nonylphenol (15 EO) 13.5 Nonylphenol(18 EO) 19.5

3. Other Currently Non-Commercially Available, Nonionic Surfactants

a. nonionic surfactant formed from α-diol condensation products;

b. polyhydroxyl nonionic compounds;

c. nonionic surfactant formed by the reaction of an ethoxylated Schiffbase with a methyl alkyl ketone;

d. i-alkyl-polyethylene−polyamines reacted with maleric acidsemiamide−nonionic compound with antibiocide properties;

e. nonionic surfactant derived from polyethoxylated alcohols+vinyl-alkylethers;

f. biodegrdeable glycidol surfactant (nonionic), e.g., alcohol+glycidol(with catalyst) producing nonionic surfactant (biodegradable);

g. multiblock polyacetal copolymer surfactants, e.g., poly-propyleneoxide or poly-ethylene oxide+dialkyl ether;

h. urea-ethoxamer nonionic inclusion compounds, e.g.,urea+polyethoxylated long chain alcohols; and

i. polyglycol ethers+polyglycol₆₀₀₀+epichlorohydrine derived nonionicsurfacts; etc.

Exemplary Applications

Some exemplary applications of the principles and compositions of thepresent invention are listed below:

1. Cleaning crude oil and petrochemical storage tanks;

2. Injection into crude oil pipelines to prevent wax or “slop”separation;

3. Add to crude oil in oceangoing vessels to prevent wax or “slop”separation;

4. As a dispersant in base lube oil stocks to lower the cloud point,namely as a dehazing compound;

5. As a wax liquefier and dispersant in base lube oil stocks to lowerthe pour point;

6. As a dispersant in gasoil to lower the cloud point, namely as adehazing compound;

7. As a wax liquefier and dispersant in gasoil to lower the pour point;

8. As a demulsifier for crude oil in pipelines and storage tanks;

9. As a wax liquefier in downhole operations in the production of crudeoil;

10. As a dispersant and degreaser in crude oil storage tanks;

11. As a dispersant and degreaser in petrochemical storage tanks;

12. As an additive in engine lubricating oil for the purpose ofdispersing lubricating oil sludge;

13. As a method of measuring the true value of crude oil by demulsifyingthe water in the crude oil; this will allow for a more accuratemeasurement of the actual amount of crude oil being purchased;

14. As a dispersant and wax liquefier in hydrocarbon liquids derivedfrom natural gas processing, i.e., condensates;

15. As a dispersant for napthenic acids in fuel oils;

16. As a dispersant for sludge in processing units such as catalyticcrackers;

17. As a dispersant for waste wax residue derived from polyethyleneplants for the purpose of dispersing the wax into fuel oil;

18. As a dispersant for wax in cutting and cooling fluids used inmachining operations;

19. As a dispersant for wax in heavy fuel oils such as, for example,“Bunker C” and Fuel Oil No. 6 (heating oil);

20. As a wax liquefier and degreaser in heat exchangers in variouspetroleum refining process units (e.g., furfural lube oil extractionplants);

21. As a dispersing agent for coke and carbon fines into hydrocarbonliquids and/or water;

22. As a dispersant for cleaning machine parts;

23. As a liquefier and dispersant for wax into hydrocarbon liquidsderived from Fischer-Tropsch synthesis;

24. As a dispersant for wax in edible oils;

25. As a dispersant for wax in organic solvents;

26. As a dispersant for asphalt in various hydrocarbon solvents;

27. As a dispersant in cutting oil emulsions;

28. As a dispersant for naturally-occurring waxes in various hydrocarbonmedia and water;

29. As a liquefier and dispersant for wax used as a protective coating;

30. As a dispersant and liquefier for wax for oil recycling processes;

31. As a dispersant for highly-paraffinic organic compounds into variousorganic solvents;

32. As a liquefier and dispersant additive in gasoline and fuel oil;

33. As a degreaser for removing asphalt from concrete surfaces;

34. As a neutral metal degreaser for metal parts in dip tanks;

35. As a liquefier for wax derived from pipeline pigging operations;

36. As a dispersant in oil for extreme pressure additives (E.P.A.);

37. As a dispersant in oil for anti-wear additives;

38. As a dispersant in lube oil to provide dispersion of products ofdegradation and combustion;

39. As a dispersant for fuel oil (e.g. “Bunker C”), diesel and gasoil;

40. As a dispersant for wax in solvent dewaxing processes;

41. As a dispersant for metals and sludge in petroleum waste products(e.g. oil/water separators);

42. As an additive for drilling muds to enhance their dispersion andsurface active activity (contact) during drilling operations;

43. As an additive in petroleum production to enhance the flow of crudein secondary and tertiary production;

44. As a wax liquefier and dispersant in the production of

a. floor coverings and polishes,

b. adhesives,

c. cosmetics,

d. electrical insulation,

e. leather finishes,

f. matches,

g. treated paper products,

h. molding and coating processes,

i. printing inks and varnishes,

j. dental materials,

k. explosives,

l. crayons,

m. textile finishes,

n. candles,

o. rubber antioxidants,

p. corrosion inhibitors, etc.;

45. As a surface active agent and dispersion in descaling formulations;

46. As a surface active agent and dispersion in acid de-rustingformulations;

47. As a wax liquefier and dispersant in high-heat distillates (e.g.lignitic tar-lignite paraffins);

48. As a dispersant for asphalt and/or tar on surface coating such as,for example, roofing paper;

49. As a cleaning chemical in the cleaning of ship ballast tanks;

50. As a wax liquefier and dispersant in emulsions used in automobileand other vehicular care products (i.e., transportation cleaners);

51. As a biodegradable dispersant for agricultural fertilizers for treesand plants;

52. As a wax liquefier and dispersant in the manufacture of grease;

53. As a dispersant for inorganic compounds in water, such as tailingsfrom mining;

54. As a dispersant and demulsifier for waste oil in oil production,exploration, transportation and refineries (A.P.I. separators); and

55. As a dispersant for wax in commercial car products to help in theself-rinsing applications; etc.

Exemplary Method for Recovering Slop Oil Tank Bottoms

At ambient temperature (e.g., 75 degrees Fahrenheit, 24 degreesCelsius), slowly add 0.13 kg (0.286 lb.) of the exemplary composition to10 kg (22 lb.) of slop oil under intense and vigorous mixing. Mix thetwo components throughly. After a homogeneous mixture has been achieved,immediately add 30 kg (66 lb.) of crude oil to the mixture of slop oiland the preferred composition. Continue mixing until a completelyhomogeneous mixture is obtained. This should take no longer than fifteen(15) minutes using the amounts specified.

During the mixing process water and sand will be observed separatingfrom the mixture. The crude oil must be added with vigorous agitationeven if water is separating during mixing. After a completelyhomogeneous mixture is obtained, cease agitation and allow the mixtureto stand for three to four (3-4) hours.

After allowing the mixture to stand for three to four (3-4) hours, aseparation layer of water and sand will be observed on the bottom of thetank; the mixture of crude oil and the composition will remain on top.The viscosity of the new hydrocarbon fraction will be low and the layerwill be completely homogenous; there should be no lumps or pieces ofparaffin floating in the hydrocarbon fraction.

Separate the water/sand layer from the mixture by, for example, pumping.The crude oil mixture may then be transferred to a storage tank and onto further processing.

Tests

A number of tests have been run showing the efficacy of the presentinvention, with the first six (6) tests using the preferred compositionor combination described above as preferred.

Test #1

The addition of 2% dispersant to one (1) barrel of slop oil/tank bottomsunder rapid mixing at 80 degrees C. (176 degrees F.), followed by theaddition of three (3) barrels of crude oil (at ambient temperature)resulted in a crude oil blend that was stable (no wax precipitates) forwell over nine (9) months.

Test #2

3% dispersant was added to one (1) barrel of slop oil/tank bottoms at 40degrees C. (104 degrees F.) under constant rapid mixing, followed by theaddition of two (2) barrels of crude oil (at ambient temperature). Theresulting product was a homogeneous and viscous blend of crude oil andslop oil/tank bottoms that showed no separation of the slop oil/tankbottoms component from the blend. The blend continues to remainhomogeneous and viscous at ambient temperature for a period so far ofwell over (9) months.

Test #3

A small sample (50 grams) of heavy waxy slop oil was taken from an oldstorage tank; the slop oil had been in the tank for over 10 years. Theslop oil was melted into a liquid mass at a temperature of approximately80 degrees C. and stirred to obtain a homogeneous mixture. 2 ml ofdispersant was added to the liquefied wax and the resulting blend wasstirred for two (2) minutes at approximately 75 degrees C.

After it was determined that the dispersant was thoroughly dispersedthroughout the liquefied wax, 150 ml of crude oil tank bottoms (anextremely viscous liquid oil fraction) was added to the mixture and theresultant blend was stirred for an additional ten (10) minutes at 75degrees C. to obtain a homogeneous mixture. The mixture was removed fromthe heat and allowed to cool down to ambient temperature (25 to 30degrees C.). After reaching ambient temperature the mixture wasseparated into two halves and poured into glass bottles for observation.Each sample indicated two layers—a clear, oil-free water layer on thebottom that contained suspended solids (sand, etc.) and an upper layerof oil.

The samples were allowed to sit for a period of 120 days during whichtime it was observed that the oil layer remained completely homogeneous.There was no separation of any solid wax material. One of the sampleswas centrifuged at ambient temperature and three (3) layers were formed:a layer of sand and grit (3%); a layer of water (27%); and a layer ofoil (70%). The oil layer remained homogeneous for a period of over 7months; there was no separation of any solid paraffin. The oil layerremains homogeneous with no separation.

Test #4

To a reactor containing 10 kg of slop oil was added 30 kg of heavyArabian crude oil containing 0.5 kg of dispersant. The mixture wasagitated to a thoroughly homogeneous state for a period of 1½ hours. Atthe end of this period 38 kg of the crude+slop hydrocarbon was pumpedout. The resulting mixture remained homogeneous for 2 weeks; a layer ofsand and water separated out of solution. The sand was pumped off andcleaned using the dispersant.

Test #5

In this test a steel machine gear heavily encrusted with hardened greaseand dirt was immersed in a solution of dispersant and water. This gearhad been stored outside, fully exposed to the elements, and had not beenhandled or moved for at least five (5) years. After being allowed tosoak in the solution for a short time, the grease and dirt softeneduntil only slight finger pressure would remove it. The solution wasagitated for a few minutes and the grease and dirt completely dispersedinto the solution. The gear was removed from the solution and thesolution was allowed to stand. The grease remained suspended in thedispersant solution.

Test #6

A 50 gm sample of wax residue from a polyethylene production plant washeated to 120 degrees C. To this heated sample was added 0.5 gms of theinvention's exemplary composition of matter. The mixture was agitateduntil complete homogeneity was observed at 120 degrees C. To the heatedmixture of polyethylene waste wax plus compound was added 200 gms offuel oil (#6 fuel).

The fuel oil was added to the mixture at 120 degrees C. This mixture wasstirred until complete homogeneity was observed at 120 degrees C. When ahomogeneous mixture was observed, the heat was taken away and themixture was allowed to cool down to room temperature. After the mixturereached room temperature, it was observed that no wax separated out ofsolution. After a period of two (2) months, still no separation of waxwas observed.

Test #7

To check for its dehazing or cloud point lowering capabilities, to asample of processed lube oil was added a modified mixture of theexemplary, usually preferred, composition of matter or product, namely,only the surface active agents (namely, polyalkylethoxylated alcoholplus nonylphenol plus a flourinated polyethoxylated alcohol) and adispersing agent polymer derived from a copolymer of partiallysulfonated, maleic anhydride and polystyrene, with the surface activeagent and the dispersing agent being present in a ratio of 200:1, namely99.5% to 0.5% by weight, was used.

At a concentration of 500 parts per million (ppm) the cloud point of thelube oil was reduced from +15 degrees C. to +3 degrees C. This test wasrepeated at a concentration of 250 ppm and then of 1,000 ppm. The cloudpoint was reduced to +6 degrees C. and +3 degrees C., respectively. Theresults are summarized in the following table.

Reduced Cloud Concentration Point (degrees C.) (ppm) from +15° C. 250 6500 3 1,000   3

Test #8

A test was performed, whereby coke from a delayed coker unit at arefinery was treated with the preferred composition of matter and aheated water mix, and the following results were obtained.:

Water plus 0.5% by weight of the invention's preferred composition ofmatter were mixed together and heated to about 200 degrees F., with thecoke in chunk form dropped into the stirred hot water and composition ofmatter mix. All of the coke treated was found to be completely dispersedin the heated mixture.

Such dispersal would not have occurred without the presence of the addedcomposition of matter of the invention.

The coke used in the test was from a stub tower and the blow-down towerfrom the delayed coker unit. The test showed that, with the coke beingin the dispersed state, the coke could be easily removed from the unitas a dispersion in water and removed from the site.

It is noted that the formulations, compositions, and applicationsdescribed herein generally and/or in detail were for exemplary purposesand are, of course, subject to many different variations. Because manyvarying and different embodiments may be made within the scope of theinventive concept(s) herein taught, and because many modifications maybe made in the embodiments herein detailed in accordance with thedescriptive requirements of the law, it is to be understood that thedetails herein are to be interpreted as illustrative and not in alimiting sense.

What is claimed is:
 1. A method of liquefying and dispersing crystallinewax, comprising the steps of: (a) chemically treating the crystallinewax to reduce the surface tension of the crystalline wax, converting itto an amorphous form of wax, by treating the crystalline wax with asurface active agent having a surface tension in water in the range ofabout 10 to about 48 dynes per cm, reducinq the crystalline wax'ssurface tension, using as the surface active agent a homogeneous mixtureincluding about 25% to about 99.9% by weight the surface active agent,and including with the surface active, agent in a homogeneous mixtureabout 15% to about 35% by weight butyl cellosolve, about 5% to about 15%by weight of pine oil and a mixed catalyst solution made of saturatedhigher fatty acids, an alkyl phenol and an oil-water soluble copolymerof partially sulfonated, maleic anhydride and polystyrene with amolecular weight ranging from about 2,000 to about 2,000,000; and (b)dispersing the amorphous wax in a diluent.
 2. The method of claim 1,wherein there is further included in step “a” the step of: treating thecrystalline wax with a surface active agent having a surface tension inwater in the range of about 15 to about 32 dynes per cm, reducing thecrystalline wax's surface tension.
 3. The method of claim 1, wherein thecrystalline wax is contained in slop oil, and there is further includedin step “b” the step of: using crude oil as the diluent.
 4. The methodof claim 3, wherein there is further included the step of: mixing theslop oil with its wax in amorphous form and the crude oil together,forming a homogeneous mixture.
 5. The method of claim 4, wherein thereis further included the step of: maintaining the homogenous mixture ofthe surface active agent, the slop oil and the crude oil together atambient temperature.
 6. The method of claim 5, wherein there is furtherincluded the step of: transporting the homogenous mixture of the surfaceactive agent, the slop oil and the crude oil together at ambienttemperature.
 7. The method of claim 4, wherein there is further includedthe step of: concurrently mixing in a degreaser in the combinedamorphous wax and diluent.
 8. The method of claim 4, wherein there isfurther included the step of: concurrently mixing in a corrosion andscale formation inhibitor in the combined amorphous wax and diluent. 9.The method of claim 4, wherein in step “b” the diluent is a refinedpetroleum product, and in step “b” there is further included the stepof: using said surface active agent as a cloud point lowering, dehazerin the combined amorphous wax and refined petroleum product.
 10. Themethod of claim 4, wherein in step “b” the diluent is a refinedpetroleum product, and in step “b” there is further included the stepof: using said surface active agent as a pour point lowering agent inthe combined amorphous wax and refined petroleum.
 11. The method ofclaim 1, wherein the diluent is crude oil, and wherein and there isfurther included the steps of: treating the crystalline wax with atreatment chemical to reduce the surface tension of the crystalline waxproducing the amorphous wax; and mixing the amorphous wax and crude oil,and retaining the treatment chemical in the mix to inhibit the formationof slop oil out of the crude oil.
 12. The method of claim 11, whereinthere is further included the step of: transporting the mixture of thetreatment chemical, the amorphous wax and the crude oil together atambient temperature.
 13. The method of claim 11, wherein there isfurther included in step “a” the step of: concurrently mixing in withthe surface active agent at least one further agent from the groupconsisting of a degreaser, a demulsifier, a corrosion inhibitor, and ascale formation inhibitor, with the treatment chemical in the combinedamorphous wax and crude oil mixture.
 14. The method of claim 11, whereinthere is further included the step of: using the surface active agent aseither a cloud point or a pour point depressant.
 15. The method of claim11, wherein there is further included the step of: mixing the treatmentchemical with the crystalline wax and crude oil at the crude oilproduction source.
 16. The method of claim 1, wherein there is furtherincluded the step of: using a catalyst mixture in a range of about 0.5%to about 5% by weight.
 17. A method of liquefying and dispersingcrystalline wax, comprising the steps of: (a) chemically treating thecrystalline wax to reduce the surface tension of the crystalline wax,converting it to an amorphous form of wax, by treating the crystallinewax with a surface active agent having a surface tension in water in therange of about 10 to about 48 dynes per cm, reducing the crystallinewax's surface tension, using as the surface active agent a homogeneousmixture, including about 25% to about 99.9% by weight the surface activeagent, including a nonionic polyethoxylated compound derived frompolyethylene oxide, and wherein the surface active agent also includes anonionic surfactant, and wherein there is further included the step ofusing, as a composition of matter mixture, a by-weight percent of thenonionic surface active agent of about 48%, with about 32% butylcellosolve and about 17% pine oil acting as degreaser, about 2% of amixture containing about 70% higher fatty acids, about 29% a copolymerof maelic anhydride and polystyrene and about 1% of catechol serving asa corrosion inhibitor; and (b) dispersing the amorphous wax in adiluent.
 18. The method of claim 17, wherein the crystalline wax iscontained in slop oil, and there is further included in step “b” thestep of: using crude oil as the diluent.
 19. The method of claim 18,wherein there is further included the step of: mixing the slop oil withits wax in amorphous form and the crude oil together, forming ahomogeneous mixture.
 20. The method of claim 19, wherein there isfurther included the step of: maintaining the homogenous mixture of thesurface active agent, the slop oil and the crude oil together at ambienttemperature.
 21. The method of claim 20, wherein there is furtherincluded the step of: transporting the homogenous mixture of the surfaceactive agent, the slop oil and the crude oil together at ambienttemperature.
 22. The method of claim 18, wherein there is furtherincluded the step of: concurrently mixing in a degreaser in the combinedamorphous wax and diluent.
 23. The method of claim 18, wherein there isfurther included the step of: concurrently mixing in a corrosion andscale formation inhibitor in the combined amorphous wax and diluent. 24.The method of claim 18, wherein in step “b” the diluent is a refinedpetroleum product, and in step “b” there is further included the stepof: using said surface active agent as a cloud point lowering, dehazerin the combined amorphous wax and refined petroleum product.
 25. Themethod of claim 18, wherein in step “b” the diluent is a refinedpetroleum product, and in step “b” there is further included the stepof: using said surface active agent as a pour point lowering agent inthe combined amorphous wax and refined petroleum.
 26. The method ofclaim 17, wherein the diluent is crude oil, and wherein and there isfurther included the steps of: treating the crystalline wax with atreatment chemical to reduce the surface tension of the crystalline waxproducing the amorphous wax; and mixing the amorphous wax and crude oil,and retaining the treatment chemical in the mix to inhibit the formationof slop oil out of the crude oil.
 27. The method of claim 26, whereinthere is further included the step of: transporting the mixture of thetreatment chemical, the amorphous wax and the crude oil together atambient temperature.
 28. The method of claim 26, wherein there isfurther included in step “a” the step of: concurrently mixing in withthe surface active agent at least one further agent from the groupconsisting of a degreaser, a demulsifier, a corrosion inhibitor, and ascale formation inhibitor, with the treatment chemical in the combinedamorphous wax and crude oil mixture.
 29. The method of claim 26, whereinthere is further included the step of: using the surface active agent aseither a cloud point or a pour point depressant.
 30. The method of claim26, wherein there is further included the step of: mixing the treatmentchemical with the crystalline wax and crude oil at the crude oilproduction source.
 31. A chemical composition of matter, comprising:wax, originally in crystalline form, but converted to an amorphous formdue to the presence of an additive including a nonionic surface activeagent, said surface active agent representing about 48% by weight;wherein there is further included about 32% butyl cellosolve and about17% pine oil, about 2% of a mixture containing about 70% higher fattyacids, about 29% a copolymer of maelic anhydride and polystyrene andabout 1% catechol.
 32. The chemical composition of claim 31, wherein:said nonionic surface active agent is a nonionic polyethoxylatedcompound.
 33. The chemical composition of claim 32, wherein: saidnonionic polyethoxylated compound is a product derived from polyethyleneoxide.
 34. A method of liquefying and dispersing crystalline wax,comprising the steps of: (a) chemically treating the crystalline waxwith a surface active agent of a nonionic surfactant that is made up ofup to about 99.9% by weight of a nonionic surfactant and down to about0.1% by weight of a surface tension depressant, thereby converting thecrystalline wax to an amorphous form of wax, using a nonionicpolyethoxylate surfactant as the nonionic surfactant and also addingwith said nonionic polyethoxylated compound in a homogeneous mixtureabout 15% to about 35% by weight butyl cellosolve, about 5% to about 15%by weight of pine oil and a mixed catalyst solution made of saturatedhigher fatty acids, an alkyl phenol and an oil-water soluble copolymerof partially sulfonated, maleic anhydride and polystyrene with amolecular weight ranging from about 2,000 to about 2,000,000.
 35. Themethod of claim 34, wherein there is further included in step “a” thestep of: using a flouronated hydrocarbon alcohol as the surface tensiondepressant.
 36. The method of claim 34, wherein there is furtherincluded in step “a” the step of: using a nonionic surfactant having aH.L.B. number ranging from about ten to about eleven and a half(10-11.5).
 37. The method of claim 34, wherein there is further includedin step “a” the step of: using a nonionic surfactant having a surfacetension in water in the range of about 10 to about 48 dynes per cm,reducing the crystalline wax's surface tension, causing it to beconverted to amorphous wax.
 38. The method of claim 34, wherein there isfurther included in step “a” the step of: using a nonionicpolyethoxylated compound as the nonionic surfactant.
 39. The method ofclaim 38, wherein there is further included in step “a” the step of:using a product derived from polyethylene oxide as the nonionicpolyethoxylated compound.
 40. The method of claim 34, wherein thecrystalline wax is contained in slop oil, and there is further includedin step “b” the step of: using crude oil as the diluent.
 41. The methodof claim 34, wherein there is further included in step “a” the step of:concurrently mixing in with the surface active agent at least oneadditional agent from the group consisting of a degreaser, ademulsifier, a corrosion inhibitor, and a scale formation inhibitor,with the treatment chemical in the combined amorphous wax and crude oilmixture.
 42. A chemical composition of matter, comprising: a by-weightpercent of a nonionic surface active agent of about 48%, with about 32%butyl cellosolve and about 17% pine oil, about 2% of a mixturecontaining about 70% higher fatty acids, about 29% a copolymer of maelicanhydride and polystyrene and about 1% of catechol.
 43. The chemicalcomposition of claim 42, wherein: said nonionic surface active agent isa nonionic polyethoxylated compound.
 44. The chemical composition ofclaim 42, wherein: said nonionic polyethoxylated compound is a productderived from polyethylene oxide.